Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
  • C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
  • C08F232/04—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2420/00—Metallocene catalysts
  • C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/62—Refractory metals or compounds thereof
  • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
  • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
  • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

• the present invention relates to a cyclic olefin copolymer, a resin composition containing the cyclic olefin copolymer, and a film-like or sheet-like molded product obtained by molding the cyclic olefin copolymer or the resin composition.
• Cyclic olefin homopolymers and cyclic olefin copolymers have low hygroscopicity and high transparency, and are used in various applications, including the field of optical materials such as optical disc substrates, optical films, and optical fibers.
• Copolymers of cyclic olefins and ethylene which are widely used as transparent resins, are known as representative cyclic olefin copolymers.
• the copolymer of cyclic olefin and ethylene can change its glass transition temperature (Tg) according to the composition of the copolymer of cyclic olefin and ethylene. Coalescing can be produced (see, for example, Non-Patent Document 1).
• a cyclic olefin copolymer for example, there is a chain site of structural units derived from a norbornene monomer, which is a cyclic olefin. It is The cyclic olefin copolymer obtained by the production method described in Non-Patent Document 1 can be obtained in both meso-type and racemo-type. On the other hand, many cyclic olefin copolymers have their stereoregularity controlled by the catalyst used for copolymerization. is of the meso type.
• the present invention has been made in view of the above-mentioned conventional problems, and its object is to provide a cyclic olefin copolymer excellent in both processability and mechanical properties, a resin composition containing the cyclic olefin copolymer, and An object of the present invention is to provide a film-like or sheet-like molded article obtained by molding the cyclic olefin copolymer or the resin composition.
• the present inventors have found that, in a cyclic olefin copolymer obtained by copolymerizing a norbornene monomer and ethylene, a chain site (two It was found that the presence of not only the meso-type but also the racemo-type in a predetermined ratio can improve the melt viscosity without sacrificing the mechanical properties. Furthermore, by simultaneously satisfying that the content of the chain site (triplet) of the structural unit derived from the norbornene monomer is equal to or less than a predetermined ratio, the mechanical properties are excellent, and the present invention has been completed. rice field.
• One aspect of the present invention for solving the above problems is as follows. (1) comprising a structural unit derived from a norbornene monomer and a structural unit derived from ethylene,
• the structural unit derived from the norbornene monomer has a meso-type bipartite moiety and a racemo-type bipartite moiety and triad moiety,
• a ratio of the content rate (mol%) of the meso-form bipartite moiety to the content rate (mol%) of the racemo-form bipartite moiety is 0.10 to 3.00
• a film-like or sheet-like molded product obtained by molding the cyclic olefin copolymer according to any one of (1) to (4) or the resin composition according to (5) above.
• a cyclic olefin copolymer excellent in both processability and mechanical properties a resin composition containing the cyclic olefin copolymer, and the cyclic olefin copolymer or the resin composition are molded. It is possible to provide a film-like or sheet-like molded product.
• the cyclic olefin copolymer of the present embodiment contains structural units derived from norbornene monomers and structural units derived from ethylene. Then, the structural unit derived from the norbornene monomer has a meso-type biad moiety and a racemo-type biad moiety and a triad moiety, and the content of the racemo-type biad moiety (mol% ) is 0.10 to 3.00, and the triad content is 2.5 mol% or less.
• the structural unit derived from the norbornene monomer contains a meso-type and a racemo-type at a predetermined ratio as the bivalent moiety, and the triad moiety has a predetermined ratio.
• the meso-type, racemo-type, and triad moieties of the norbornene monomer-derived structural unit are shown in the following structures.
• the ratio of the content (mol%) of the meso-type bipartite moiety to the content (mol%) of the racemo-type bipartite moiety is 0.10 to 0.10. 3.00. If the value of the ratio is less than 0.10, the mechanical properties, ie, toughness, are degraded, and if it exceeds 3.00, the melt viscosity is increased and workability is degraded.
• the value of the ratio is preferably 0.20 to 2.5, more preferably 0.20 to 2.0, still more preferably 0.20 to 1.5, even more preferably 0.20 to 1.0. 0.20 to 0.90 is particularly preferred, and 0.20 to 0.60 is most preferred.
• the total content of the racemo-type biad moiety and the meso-type biad moiety is preferably 0.1 to 10 mol%, more preferably 0.2 to 8 mol%, and further 0.3 to 7 mol%. preferable.
• the content of triad moieties in structural units derived from norbornene monomers in the cyclic olefin copolymer is 2.5 mol % or less. If the content exceeds 2.5 mol %, the mechanical properties, that is, the toughness, are lowered, and the workability is lowered.
• the content is preferably 2.3 mol % or less, more preferably 2.0 mol % or less.
• the lower limit of the content of the triad moiety is preferably 0 mol %.
• the ratio of the content (mol%) of the meso-type bipartite moiety to the content (mol%) of the racemo-type bipartite moiety is 13C . —obtained by identifying each site by NMR, calculating the ratio (mol%), and dividing the ratio of the meso-type biadultaneous moiety by the ratio of the racemo-type biadultaneous moiety.
• the content of the triad moiety of the structural unit derived from the norbornene monomer is determined by identifying the triad moiety by 13 C-NMR and determining the ratio (mol%). It is obtained by calculating
• the ratio of the content ratio (mol%) of the meso-type bipartite moiety to the content ratio (mol%) of the racemo-type bipartite moiety is set to 0.10 to 3.00, and
• the content of 2.5 mol% or less relative to the cyclic olefin copolymer can be realized by, for example, copolymerizing a norbornene monomer and ethylene using a predetermined catalyst having a phosphine imide group. , which will be discussed later.
• the ratio of the content (mol%) of the meso-type bipartite moiety to the content (mol%) of the racemo-type bipartite moiety is 0.10 to 0.10. 3.00, and the ratio of the meso-type bipartite moiety tends to be smaller than the ratio of the racemo-type bipartite moiety.
• the mechanical properties are the same as those of conventional cyclic olefin copolymers in which meso-type bipartite moieties occupy the majority.
• the cyclic olefin copolymer of the present embodiment has a glass transition temperature of 110° C. or lower. That is, when the glass transition temperature of the cyclic olefin copolymer is 110° C. or less, the amount of norbornene in the copolymer is small and the flexible ethylene units are sufficiently large. Therefore, although it has a structure that is sterically disadvantageous in terms of mechanical properties, it is thought that it has little effect on mechanical properties due to the flexibility of the ethylene unit with a sufficient content. Therefore, the glass transition temperature of the cyclic olefin copolymer of the present embodiment is preferably 110°C or less, more preferably 10 to 100°C.
• the content of triad sites in structural units derived from norbornene monomers is 2.5 mol % or less relative to the cyclic olefin copolymer.
• the ratio of the content ratio (mol%) of the meso-form bipartite moiety to the content ratio (mol%) of the racemo-form bipartite moiety is 0.10 to 3.00, and
• the cyclic olefin copolymer of the present embodiment has excellent mechanical properties because the triad moiety content is 2.5 mol % or less.
• the structural unit derived from the norbornene monomer has a meso-type bipartite moiety and a racemo-type bipartite moiety at a predetermined ratio, and has a triad moiety at a predetermined ratio.
• the cyclic olefin copolymer to be contained can be obtained by the following production method.
• the production method includes at least a step of charging a norbornene monomer and ethylene as monomers into a polymerization vessel (hereinafter referred to as a “charge step”), and a catalyst having a phosphineimide group with the monomers in the polymerization vessel. and a step of polymerizing in the presence (hereinafter referred to as a “polymerization step”). Each step will be described in detail below.
• the charging step at least the norbornene monomer and ethylene are charged into the polymerization vessel as monomers.
• the polymerization vessel may be charged with monomers other than the norbornene monomer and ethylene as long as they do not adversely affect the production method of the present embodiment.
• the sum of the ratio of structural units derived from norbornene monomer and the ratio of structural units derived from ethylene is typically 80% by mass or more with respect to all structural units. It is preferably 95% by mass or more, more preferably 98% by mass or more.
• the method of charging ethylene into the polymerization solution is not particularly limited as long as the desired amount of ethylene can be charged into the polymerization vessel.
• ethylene is charged to the polymerization vessel such that the charging pressure of ethylene in the polymerization vessel is 0.5 MPa or higher.
• the charging pressure of ethylene is preferably 0.55 MPa or higher, more preferably 0.6 MPa or higher.
• the charging pressure of ethylene is, for example, preferably 10 MPa or less, more preferably 5 MPa or less, and even more preferably 3 MPa or less.
• a solvent may be charged into the polymerization vessel together with the norbornene monomer and ethylene.
• the solvent is not particularly limited as long as it does not inhibit the polymerization reaction.
• solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), benzene, toluene, and xylene, chloroform, methylene chloride. , dichloromethane, dichloroethane, and halogenated hydrocarbon solvents such as chlorobenzene.
• the lower limit of the concentration of the norbornene monomer is, for example, preferably 0.5% by mass or more, more preferably 10% by mass or more.
• the upper limit is, for example, preferably 50% by mass or less, more preferably 35% by mass or less.
• the norbornene monomer will be described in detail below.
• Norbornene monomers include, for example, norbornene and substituted norbornenes, with norbornene being preferred.
• a norbornene monomer can be used individually by 1 type or in combination of 2 or more types.
• substituted norbornene is not particularly limited, and examples of substituents possessed by this substituted norbornene include halogen atoms and monovalent or divalent hydrocarbon groups.
• substituents possessed by this substituted norbornene include halogen atoms and monovalent or divalent hydrocarbon groups.
• Specific examples of substituted norbornenes include compounds represented by the following general formula (I).
• R 1 to R 12 may be the same or different, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, R 9 and R 10 , R 11 and R 12 may combine to form a divalent hydrocarbon group, R 9 or R 10 and R 11 or R 12 may form a ring together.
• R 1 to R 12 in general formula (I) may be the same or different and are selected from the group consisting of hydrogen atoms, halogen atoms and hydrocarbon groups.
• R 1 to R 8 include hydrogen atoms; halogen atoms such as fluorine, chlorine and bromine; alkyl groups having 1 to 20 carbon atoms; , may be partially different, or all may be the same.
• R 9 to R 12 include hydrogen atom; halogen atom such as fluorine, chlorine and bromine; alkyl group having 1 to 20 carbon atoms; cycloalkyl group such as cyclohexyl group; substituted or unsubstituted aromatic hydrocarbon groups such as groups, ethylphenyl groups, isopropylphenyl groups, naphthyl groups, and anthryl groups; benzyl groups, phenethyl groups, and other aralkyl groups in which alkyl groups are substituted with aryl groups; These may be different, partially different, or all may be the same.
• R 9 and R 10 or R 11 and R 12 are combined to form a divalent hydrocarbon group
• alkylidene groups such as ethylidene group, propylidene group and isopropylidene group. can be mentioned.
• the ring formed may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge. , a ring having a double bond, or a ring consisting of a combination of these rings. Moreover, these rings may have a substituent such as a methyl group.
• substituted norbornenes represented by general formula (I) include 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hepta- 2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.
• alkyl-substituted norbornenes e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups
• alkylidene-substituted norbornenes e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkylidene groups
• [2.2.1]hept-2-ene) is preferred, and 5-ethylidene-bicyclo[2.2.1]hept-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidenenorbornene) ) is particularly preferred.
• the norbornene monomer and monomers other than ethylene are not particularly limited as long as they are copolymerizable with the norbornene monomer and ethylene.
• Typical examples of such other monomers include ⁇ -olefins.
• the ⁇ -olefin may be substituted with at least one substituent such as a halogen atom.
• C3 to C12 ⁇ -olefins are preferred.
• the C3 to C12 ⁇ -olefins are not particularly limited, but examples include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1 -pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl -1-hexene, 1-octene, 1-decene, 1-dodecene and the like. Among them, 1-hexene, 1-octene and 1-decene are preferred.
• the monomers in the polymerization vessel are polymerized in the presence of a specific catalyst having a phosphine imide group.
• the temperature during polymerization is not particularly limited.
• the temperature during polymerization is preferably 20° C. or higher, more preferably 30° C. or higher, still more preferably 50° C. or higher, and even more preferably 60° C. or higher, because the yield of the cyclic olefin copolymer is good. 70° C. or higher is particularly preferred.
• the temperature during polymerization may be 80° C. or higher, or may be 85° C. or higher.
• the upper limit of the temperature during polymerization is not particularly limited.
• the upper limit of the temperature during polymerization may be, for example, 200° C. or lower, 140° C. or lower, or 120° C. or lower.
• Catalyst having a phosphine imide group As the catalyst having a phosphineimide group (hereinafter referred to as "catalyst A”), it is preferable to use a metal-containing compound represented by the following formula (a1).
• the constitutional unit derived from the norbornene monomer contains a meso-type biadult site and a racemo-type biadate site at a predetermined ratio, and a triad site is a predetermined cyclic olefin copolymers can be produced.
• M is Ti, Zr, or Hf, and Ti and Zr are particularly preferred from the viewpoints of the availability and production of the catalyst A, the activity of the catalyst, and the like.
• M is Zr, from the viewpoint of improving the catalytic activity, it is preferable to bring the catalyst and the alkylaluminum compound into contact in advance (after mixing) before adding them to the polymerization system.
• the alkylaluminum compound for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, MAO (generally containing alkylaluminum), etc. are preferably used.
• the amount of the alkylaluminum compound mixed with the catalyst is preferably 1 to 100 equivalents, more preferably 2 to 50 equivalents, even more preferably 2 to 10 equivalents, relative to the catalyst.
• X is an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or a halogen atom.
• L 1 is a group represented by the following formula (a1a) or formula (a1b).
• L2 is a group represented by the following formula (a1b).
• L 1 and L 2 may be the same group or different groups, and are preferably the same group. .
• R a1 to R a5 may each independently be the same or different and represent a hydrogen atom, an organic substituent having 1 to 3 carbon atoms which may contain a heteroatom, or an inorganic substituent. is the base. Two groups of R a1 to R a5 adjacent to each other on the 5-membered ring may be bonded to each other to form a ring.
• R a6 to R a8 may be the same or different, and may each independently represent a hydrogen atom, an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or an inorganic substituent. is the base. Two groups selected from R a6 to R a8 may bond together to form a ring.
• X is an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or a halogen atom.
• the organic substituent having 1 to 20 carbon atoms which may contain a heteroatom when the organic substituent contains a heteroatom, the type of the heteroatom is particularly within a range that does not impede the effects of the production method of the present embodiment. Not limited. Specific examples of heteroatoms include oxygen, nitrogen, sulfur, phosphorus, silicon, selenium, and halogen atoms.
• the organic substituent is not particularly limited as long as it does not inhibit the formation reaction of the metal-containing compound represented by the above formula (a1).
• alkyl groups having 1 to 6 carbon atoms alkoxy groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, and aliphatic acyl groups having 2 to 6 carbon atoms.
• benzoyl, phenyl, benzyl, phenethyl, trialkylsilyl groups having 3 to 10 carbon atoms and triarylsilyl groups having 3 to 10 carbon atoms are preferred.
• a silyl group, a triphenylsilyl group, and a trispentafluorophenylsilyl group are more preferred.
• X is preferably a halogen atom, more preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.
• R a1 to R a5 may each independently be the same or different and represent a hydrogen atom, an organic substituent having 1 to 3 carbon atoms which may contain a heteroatom, or an inorganic substituent. is the base.
• Two groups of R a1 to R a5 adjacent to each other on the 5-membered ring may be bonded to each other to form a ring.
• Specific examples and preferred examples of organic substituents having 1 to 3 carbon atoms which may contain a heteroatom as R a1 to R a5 are each a carbon atom which may contain a heteroatom as X
• Specific examples and preferred examples of organic substituents of numbers 1 to 3 are the same.
• the inorganic substituent is not particularly limited as long as it does not inhibit the formation reaction of the metal-containing compound represented by the above formula (a1).
• Specific examples of inorganic substituents include halogen atoms, nitro groups, unsubstituted amino groups, cyano groups, and the like.
• R a6 to R a8 may be the same or different, and may each independently represent a hydrogen atom, an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or an inorganic substituent. is the base.
• two groups selected from R a6 to R a8 may bond together to form a ring.
• Specific examples and preferred examples of organic substituents having 1 to 20 carbon atoms which may contain a heteroatom as R a6 to R a8 are each a carbon atom which may contain a heteroatom as X
• Specific examples and preferred examples of organic substituents of numbers 1 to 20 are the same.
• R a6 to R a8 an adamantyl group and an o-tolyl group are also preferable examples of the organic substituent having 1 to 20 carbon atoms which may contain a heteroatom.
• the organic substituent having 1 to 20 carbon atoms which may contain a hetero atom as R a6 to R a8 is a group represented by formula (a1b), which is R a6 to R a8
• groups each independently being a hydrocarbon group having 1 to 20 carbon atoms are also preferred.
• Me is a methyl group
• Et is an ethyl group
• n-Pr is an n-propyl group
• iso-Pr is an iso-propyl group
• n-Bu is an n-butyl group
• iso -Bu is an isobutyl group
• sec-Bu is a sec-butyl group
• tert-Bu is a tert-butyl group
• Ph is a phenyl group.
• R a6 to R a8 are preferably cyclic or non-cyclic tertiary alkyl groups or aromatic ring groups having at least one alkyl group at the ortho position.
• Cyclic tertiary alkyl groups include adamantyl groups and the like, and non-cyclic tertiary alkyl groups include tert-butyl groups and the like.
• aromatic ring group having at least one or more alkyl groups at the ortho position include o-tolyl group and mesityl group.
• Preferred specific examples of the metal-containing compound represented by the formula (a1) described above include the following metal-containing compounds.
• M in the following formula is the same as M in formula (a1).
• Si(Me) 3 is a trimethylsilyl group
• Si(Me) 2 tert-butyl is a tert-butyldimethylsilyl group.
• the above catalyst having a phosphineimide group preferably has a cyclopentadiene ring, and the cyclopentadiene ring is preferably unsubstituted or has at least one of a methyl group and a trimethylsilyl group as a substituent.
• L 1 includes a group represented by formula (a1a)
• R a1 to R a5 in formula (a1a) are at least one of a hydrogen atom, a methyl group, and a trimethylsilyl group. Those with seeds fall under this category.
• the polymerization of the monomers is preferably carried out in the presence of the catalyst A and co-catalyst.
• the co-catalyst compounds generally used as co-catalysts in the polymerization of olefins can be used without particular limitation. Suitable examples of co-catalysts include aluminoxanes and ionic compounds.
• the polymerization of the monomers is preferably carried out using at least one of an aluminoxane and a borate compound as an ionic compound as a cocatalyst because the polymerization reaction tends to proceed well.
• the above catalyst A is preferably mixed with an aluminoxane and/or an ionic compound to form a catalyst composition.
• the ionic compound is a compound that reacts with the catalyst A to produce a cationic transition metal compound.
• the catalyst composition is preferably prepared using a solution of catalyst A.
• the solvent contained in the solution of catalyst A is not particularly limited.
• Preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), mineral oil, benzene, toluene, and xylene, chloroform, Halogenated hydrocarbon solvents such as methylene chloride, dichloromethane, dichloroethane, and chlorobenzene are included.
• the amount of solvent used is not particularly limited as long as a catalyst composition with desired performance can be produced.
• the concentrations of catalyst A, aluminoxane, and ionic compound are preferably 0.00000001 to 100 mol/L, more preferably 0.00000005 to 50 mol/L, and particularly preferably 0.0000001 to 20 mol/L. amount of solvent is used.
• the number of moles of the transition metal element in the catalyst A is M a
• the number of moles of aluminum in the aluminoxane is M b1
• the number of moles of the ionic compound is M b2 .
• the value of (M b1 +M b2 )/M a is preferably 1 to 200,000, more preferably 5 to 100,000, and particularly preferably 10 to 80,000. preferably.
• the temperature at which the liquid containing the raw materials of the catalyst composition is mixed is not particularly limited, but -100 to 100°C is preferable, and -50 to 50°C is more preferable.
• Mixing of the solution of catalyst A, the aluminoxane, and/or the ionic compound for preparing the catalyst composition may be performed in a device separate from the polymerization vessel before polymerization. It may be done before or during the polymerization.
• aluminoxane As the aluminoxane, various aluminoxanes conventionally used as co-catalysts in the polymerization of various olefins can be used without particular limitation. Typically the aluminoxane is an organic aluminoxane. In the production of the catalyst composition, the aluminoxanes may be used singly or in combination of two or more.
• an alkylaluminoxane is preferably used as the aluminoxane.
• alkylaluminoxanes include compounds represented by the following formula (b1-1) or (b1-2).
• An alkylaluminoxane represented by the following formula (b1-1) or (b1-2) is a product obtained by reacting trialkylaluminum with water.
• R represents an alkyl group having 1 to 4 carbon atoms; n represents an integer of 0 to 40, preferably 2 to 30; ]
• alkylaluminoxanes examples include methylaluminoxane and modified methylaluminoxane obtained by substituting part of the methyl groups of methylaluminoxane with other alkyl groups.
• modified methylaluminoxane for example, modified methylaluminoxane having an alkyl group having 2 to 4 carbon atoms such as an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group as an alkyl group after substitution is preferable, and in particular, Modified methylaluminoxane in which part of the methyl groups are substituted with isobutyl groups is more preferred.
• alkylaluminoxane examples include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Among them, methylaluminoxane and methylisobutylaluminoxane are preferred.
• the alkylaluminoxane can be prepared by a known method. Moreover, you may use a commercial item as an alkylaluminoxane. Examples of commercially available alkylaluminoxanes include MMAO-3A, TMAO-200 series, TMAO-340 series, solid MAO (all manufactured by Tosoh Finechem Co., Ltd.), and methylaluminoxane solution (manufactured by Albemarle). .
• An ionic compound is a compound that reacts with catalyst A to form a cationic transition metal compound.
• Such ionic compounds include the anion of tetrakis(pentafluorophenyl)borate, amine cations with active protons such as the dimethylphenylammonium cation ((CH 3 ) 2 N(C 6 H 5 )H + ), (C 6 H 5 )
• Ionic compounds containing ions such as trisubstituted carbonium cations such as 3C + , carborane cations, metal carborane cations, ferrocenium cations with transition metals can be used.
• a suitable example of the ionic compound is borate.
• Preferred specific examples of borates include tetrakis(pentafluorophenyl)tritylborate, dimethylphenylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, and N-methyldi-normaldecyl N-methyldialkylammonium tetrakis(pentafluorophenyl)borate such as ammonium tetrakis(pentafluorophenyl)borate.
• aluminoxanes and alkylaluminum compounds are selected into the polymerization vessel. It is preferred to have one or more present.
• the aluminoxane is as described in the method for producing the catalyst composition.
• the alkylaluminum compound compounds conventionally used for polymerization of olefins can be used without particular limitation.
• alkylaluminum compounds include compounds represented by the following general formula (II). (R 10 ) z AlX 3-z (II) (In general formula (II), R 10 is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 8 carbon atoms, X is a halogen atom or a hydrogen atom, and z is an integer of 1 to 3. )
• alkyl groups having 1 to 15 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and n-octyl group.
• alkylaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, and tri-n-octylaluminum; dialkylaluminum halides such as aluminum chloride and diisobutylaluminum chloride; dialkylaluminum hydrides such as diisobutylaluminum hydride; and dialkylaluminum alkoxides such as dimethylaluminum methoxide.
• trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, and tri-n-octylaluminum
• the amount used is preferably 1 to 1,000,000 mol, preferably 10, as the number of moles of aluminum in the aluminoxane per 1 mol of the catalyst A. ⁇ 100,000 moles is more preferred.
• the amount used is preferably 1 to 500,000 mol, preferably 10 to 500,000 mol, in terms of the number of moles of aluminum per 1 mol of the catalyst A. 50000 mol is more preferred.
• Polymerization is preferably carried out in the presence of catalyst A and aluminoxane, or in the presence of catalyst A, an ionic compound, and alkylaluminum.
• Polymerization conditions are not particularly limited as long as a cyclic olefin copolymer having desired physical properties can be obtained, and known conditions can be used.
• the amount of catalyst composition used is derived from the amount of metal-containing compound used in its preparation.
• the amount of the catalyst composition used is preferably 0.000000001 to 0.005 mol, more preferably 0.00000001 to 0.0005 mol, relative to 1 mol of the norbornene monomer, as the mass of the metal-containing compound used for its preparation. more preferred.
• the polymerization time is not particularly limited, and the polymerization is carried out until the desired yield is reached or the molecular weight of the polymer is increased to the desired extent.
• the polymerization time varies depending on the temperature, catalyst composition, and monomer composition, but is typically 0.01 to 120 hours, preferably 0.1 to 80 hours, and 0.2 to 80 hours. 10 hours is more preferred.
• At least a portion, preferably all, of the catalyst composition is added continuously to the polymerization vessel.
• continuously adding the catalyst composition continuous production of the cyclic olefin copolymer becomes possible, making it possible to reduce the production cost of the cyclic olefin copolymer.
• the cyclic olefin copolymer produced by the above method has excellent workability and mechanical properties (toughness). Therefore, the cyclic olefin copolymer produced by the above method can be used as a functional packaging film or sheet for packaging materials such as optical films or optical sheets, shrink packaging films, pharmaceutical packaging, medical device packaging, food packaging, etc. is particularly preferably used as a material for packaging materials.
• polyolefins such as polyethylene and polypropylene, elastomers such as styrene elastomers, etc. are added at the time of plant addition or compounding in order to improve film processability. It may be blended by various methods and subjected to processing such as molding.
• the resin composition of the present embodiment contains the above cyclic olefin copolymer of the present embodiment. Since the resin composition of the present embodiment contains the cyclic olefin copolymer of the present embodiment, the resin composition and molded articles obtained by molding the resin composition are excellent in both workability and mechanical properties. can get.
• the resin composition of the present embodiment preferably further contains an antioxidant.
• an antioxidant By containing an antioxidant, decomposition/degradation and yellowing of the resin composition during processing can be suppressed.
• antioxidants can be used singly or in combination of two or more.
• antioxidants include hindered phenol-based antioxidants and phenol-based antioxidants.
• antioxidants may be used in combination with an antioxidant such as a hindered amine antioxidant or a sulfur compound.
• hindered phenol antioxidants include 2,6-di-tert-butyl-p-cresol, stearyl-(3,5-dimethyl-4-hydroxybenzyl)thioglycolate, stearyl- ⁇ -(4-hydroxy-3,5-di-tert-butylphenyl)propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, distearyl (4-hydroxy-3-methyl- 5-tert-butyl)benzylmalonate, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 4,4′-methylenebis(2,6-di-tert-butylphenol), 2,2′ -methylenebis[6-(1-methylcyclohexyl)-p-cresol], bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester, 4,4'-butylidenebis
• the antioxidant content in the resin composition is preferably 0.01 to 5% by mass, more preferably 0.1 to 1% by mass.
• the resin composition of the present embodiment is generally added to thermoplastic resins and thermosetting resins in order to impart desired properties according to the purpose, within a range that does not impair its effects.
• known additives i.e. release agents, lubricants, plasticizers, flame retardants, colorants such as dyes and pigments, crystallization accelerators, crystal nucleating agents, heat stabilizers, weather stabilizers, corrosion inhibitors, etc. may be blended.
• the film-like or sheet-like molded article of the present embodiment is formed by molding the cyclic olefin copolymer of the present embodiment or the resin composition of the present embodiment.
• the cyclic olefin copolymer of the present embodiment is excellent in workability and mechanical properties (toughness). Therefore, it is easy to mold into a film-like or sheet-like shape.
• the resulting film-like or sheet-like molded product has excellent mechanical properties (toughness).
• the film-like or sheet-like molded article of the present embodiment can be obtained by using a T-shaped die to obtain the above-described cyclic olefin copolymer alone or a composition to which other resin components or additives are added as necessary. It can be obtained by molding into a film or sheet by known extrusion molding such as extrusion molding.
• Examples 1 to 7, Comparative Examples 1 to 2 In each example and comparative example, 157 kg of decalin and 23 kg of norbornene were added to a 1 m 3 SUS polymerizer that was sufficiently nitrogen-substituted under a nitrogen atmosphere, and then TIBA (triisobutyl aluminum (Tosoh Finechem (Tosoh Finechem)) was used as cocatalyst 1. Co., Ltd.)/toluene solution (1 mol/L)) was added in an amount shown in Table 1 (excluding Example 4 and Comparative Examples 1 and 2). Then, ethylene was passed through the polymerizer to saturate it.
• TIBA triisobutyl aluminum (Tosoh Finechem (Tosoh Finechem)
• Example 6 TMAO (see below) was slowly added dropwise to catalyst 6 (toluene solution) so that the amount of trimethylaluminum added was 3 equivalents relative to the amount of catalyst, followed by stirring at room temperature for 1 hour. was added at the amount of catalyst used shown in Table 1.
• Example 7 a toluene solution of trimethylaluminum was slowly added dropwise to catalyst 7 (toluene solution) so that the amount of trimethylaluminum added was 3 equivalents relative to the amount of catalyst, followed by stirring at room temperature for 1 hour.
• TMAO is a TMAO-211 toluene solution (9.0% by mass (as Al atom content) solution of methylaluminoxane, manufactured by Tosoh Finechem Co., Ltd., and 26 mol% of trimethylaluminum based on total Al).
• MMAO is MMAO-3A toluene solution (6.5% by weight (as content of Al atoms) [(CH 3 ) 0.7 (iso-C 4 H 9 ) 0.3 AlO]
• n methylisobutylaluminoxane represented by n , manufactured by Tosoh Finechem Co., Ltd., containing 6 mol % of trimethylaluminum relative to the total Al
• Table 1 shows that the cyclic olefin copolymers of Examples 1 to 7 have low melt viscosities, high tensile yield elongation and tensile breaking elongation, and excellent toughness (mechanical properties). That is, the cyclic olefin copolymers of Examples 1 to 7 are excellent in both processability and mechanical properties.
• the ratio of the content ratio (mol%) of the meso-type bipartite moiety to the content ratio (mol%) of the racemo-type bipartite moiety is in a particularly preferable range.

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